Glassy carbon electrode modified with gold nanoparticles and hemoglobin in a chitosan matrix for improved pH-switchable sensing of hydrogen peroxide

Hemoglobin (Hb) has been demonstrated to endow electrochemical sensors with pH-switchable response because of the presence of carboxyl and amino groups. Hb was deposited in a chitosan matrix on a glassy carbon electrode (GCE) that was previously coated with clustered gold nanoparticles (Au-NPs) by electrodeposition. The switching behavior is active (“on”) to the negatively charged probe [Fe(CN)₆ ³⁻] at pH 4.0, but inactive (“off”) to the probe at pH 8.0. This switch is fully reversible by simply changing the pH value of the solution and can be applied for pH-controlled reversible electrochemical reduction of H₂O₂ catalyzed by Hb. The modified electrode was tested for its response to the different electroactive probes. The response to these species strongly depends on pH which was cycled between 4 and 8. The effect is also attributed to the presence of pH dependent charges on the surface of the electrode which resulted in either electrostatic attraction or repulsion of the electroactive probes. The presence of Hb, in turn, enhances the pH-controllable response, and the electrodeposited Au-NPs improve the capability of switching. This study reveals the potential of protein based pH-switchable materials and also provides a simple and effective strategy for fabrication of switchable chemical sensors as exemplified in a pH-controllable electrode for hydrogen peroxide.

A pH “on-off” switchable nanobiosensor was fabricated by casting a chitosan-hemoglobin biocomposite onto nano-gold electrode. This composite film exhibits not only excellent pH-responsive on (pH 4.0)-off (pH 8.0) behavior but also excellent pH-tunable on-off bioelectrocatalysis of H₂O₂.

     

Electrodeposition and characterization of Zn–Sn alloy coatings from a deep eutectic solvent based on choline chloride for corrosion protection

With the aim of obtaining high corrosion resistant Zn–Sn alloy coatings from an ionic liquid, the effects of electrodeposition potential and electrolyte composition on the electrodeposition behavior, film composition, morphology and corrosion performance were investigated. Cyclic voltammograms indicate that Zn and Sn were co‐deposited at distinct reduction potentials as pure Zn and Sn elements. In addition, the phase composition analysis also showed that the obtained Zn–Sn alloy deposits (8 wt.%–45 wt.% Zn) consist of a two‐phase mechanical mixture of small aggregates of Zn and Sn metals. The Zn content of the alloy significantly increases as the electrodeposition potential and electrolyte Zn (II)/Sn (II) ratio increase. The corrosion performance study of the obtained Zn–Sn coatings showed that they have a passivation behavior and their corrosion resistance increases as the alloy‐Sn content increases. To improve their morphological properties, ethylene diamine tetraacetic acid additive was introduced into the electrolyte and greatly improved the morphology and corrosion resistance of the deposits. For the first time, it was shown that high corrosion resistance Zn–Sn coatings can be obtained from ionic liquids. Copyright © 2014 John Wiley & Sons, Ltd.     

紫外光引发环氧树脂的下行前线聚合行为

采用紫外光(UV)引发法研究了221型脂环族环氧树脂的下行前线聚合行为.探讨了光引发剂、热引发剂用量和预热温度等对聚合前线的推动速率Vf和前线引发时间ti的影响,并利用傅里叶变换红外光谱(FTIR)、热重(TG)和差示扫描量热(DSC)等对固化物结构和热性能进行了表征.研究结果表明,提高光引发剂浓度、热引发剂浓度或预热温度,均可提高聚合前线的推动速率Vf,缩短引发时间ti.采用该技术制备的环氧树脂固化物具有较好的均一性及热稳定性.     

Functional graphene-gold nano-composite fabricated electrochemical biosensor for direct and rapid detection of bisphenol A

In this research, the graphene with excellent dispersity is prepared successfully by introducing gold nanoparticle to separate the individual sheets. Various techniques are adopted to characterize the prepared graphene and graphene-gold nanoparticle composite materials. This fabricated new composite material is used as the support material to construct a novel tyrosinase based biosensor for detection of bisphenol A (BPA). The electrochemical performances of the proposed new enzyme biosensor were investigated by differential pulse voltammetry (DPV) method. The proposed biosensor exhibited excellent performance for BPA determination with a wide linear range (2.5 × 10⁻³–3.0 μM), a highly reproducible response (RSD of 2.7%), low interferences and long-term stability. And more importantly, the calculated detection limit of the proposed biosensor was as low as 1 nM. Compared with other detection methods, this graphene-gold nanoparticle composite based tyrosinase biosensor is proved to be a promising and reliable tool for rapid detection of BPA for on-site analysis of emergency BPA related pollution affairs.     

Rapid determination of products of phenol hydrogenation in a supercritical water system using headspace gas chromatography

This paper reports a headspace analysis technique for the determination of products, i.e., cyclohexanone (CE) and cyclohexanol (CL), of phenol hydrogenation in a supercritical water reaction system (SWRS) with water removal by hydrate formation. An addition of anhydrous calcium chloride leads to water absorption resulting in crystal water; thus, the samples can be quantitatively measured without the influence of water. After achieving equilibrium at 150°C and maintaining it for 5 min, the obtained results showed a relative standard deviation of less than 5.3% and the recovery ranged from 93% to 104%. The presented method is simple and accurate for the analysis of CL, CE and phenol in samples from phenol conversion in SWRS.     

自然光照下PEG/PAA凝胶在Fe~(3+)/CA溶液中的凝胶-溶胶转化行为

将PEG/PAA凝胶浸入铁/柠檬酸(Fe3+/CA)溶液中,自然光照一定时间可实现凝胶-溶胶的相互转化,而且转化行为受溶液的组成及其p H影响。只有当溶液中[Fe3+]0∶[CA]0≤1∶2,且溶液的p H在1~6之间,该转化才会发生,通过改变溶液中[Fe3+]0∶[CA]0的值或溶液的p H可以有效地控制其转化速率。此外,结果还表明,当凝胶转化为溶胶后,向其中加入高价金属阳离子,例如Fe3+、Al3+、Ce4+、Cu2+等,溶胶又会再次转化为凝胶。由于这种新颖的特性,该凝胶有望应用于药物释放、细胞培养等领域。     

Cobalt‐Catalyzed Cross‐Coupling of 3‐ and 4‐Iodopiperidines with Grignard Reagents

A cobalt‐catalyzed cross‐coupling between 3‐ and 4‐iodopiperidines and Grignard reagents is disclosed. The reaction is an efficient, cheap, chemoselective, and flexible way to functionalize piperidines. This coupling was used as the key step to realize a short synthesis of (±)‐preclamol. Some mechanistic investigations were conducted that highlight the formation of radical intermediates.     

Unexpectedly Simple Synthesis of Benzazoles by tBuONa‐Catalyzed Direct Aerobic Oxidative Cyclocondensation of o‐Thio/Hydroxy/Aminoanilines with Alcohols under Air

tBuONa‐catalyzed direct aerobic oxidative cyclocondensation reactions of readily available alcohols and o‐thio/hydroxy/aminoanilines under air have been developed and provide an efficient, practical, and green method for the synthesis of benzazoles. Mechanistic studies revealed that o‐substituted anilines promote the initial aerobic alcohol‐oxidation step, which explains the high reactivity and success of this unexpectedly simple and practical cyclocondensation method.